JP4348203B2 - Rubber-like latex-containing foamed styrene resin molded article and method for producing the same - Google Patents
Rubber-like latex-containing foamed styrene resin molded article and method for producing the same Download PDFInfo
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims description 120
- 229920000126 latex Polymers 0.000 title claims description 81
- 239000004816 latex Substances 0.000 title claims description 71
- 229920005989 resin Polymers 0.000 title claims description 70
- 239000011347 resin Substances 0.000 title claims description 70
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000002245 particle Substances 0.000 claims description 62
- 238000000465 moulding Methods 0.000 claims description 24
- 229920001577 copolymer Polymers 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- 229920001890 Novodur Polymers 0.000 claims description 15
- 229920001971 elastomer Polymers 0.000 claims description 12
- 239000005060 rubber Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000006260 foam Substances 0.000 claims description 9
- 239000000975 dye Substances 0.000 claims description 7
- 239000000049 pigment Substances 0.000 claims description 7
- 239000013008 thixotropic agent Substances 0.000 claims description 7
- 239000003242 anti bacterial agent Substances 0.000 claims description 5
- 229920006174 synthetic rubber latex Polymers 0.000 claims description 4
- 239000004599 antimicrobial Substances 0.000 claims description 2
- 238000005187 foaming Methods 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- -1 or the like Natural products 0.000 description 11
- 229920003048 styrene butadiene rubber Polymers 0.000 description 10
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 5
- 229920006248 expandable polystyrene Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 230000003139 buffering effect Effects 0.000 description 3
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical class C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000004794 expanded polystyrene Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 201000009030 Carcinoma Diseases 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 239000001045 blue dye Substances 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000001044 red dye Substances 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- HVTQDSGGHBWVTR-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-phenylmethoxypyrazol-1-yl]-1-morpholin-4-ylethanone Chemical compound C(C1=CC=CC=C1)OC1=NN(C=C1C=1C=NC(=NC=1)NC1CC2=CC=CC=C2C1)CC(=O)N1CCOCC1 HVTQDSGGHBWVTR-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 241000047703 Nonion Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 241000219315 Spinacia Species 0.000 description 1
- 235000009337 Spinacia oleracea Nutrition 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- HWQXBVHZYDELQG-UHFFFAOYSA-L disodium 2,2-bis(6-methylheptyl)-3-sulfobutanedioate Chemical compound C(CCCCC(C)C)C(C(C(=O)[O-])S(=O)(=O)O)(C(=O)[O-])CCCCCC(C)C.[Na+].[Na+] HWQXBVHZYDELQG-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229920001821 foam rubber Polymers 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920006327 polystyrene foam Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000011032 tourmaline Substances 0.000 description 1
- 229940070527 tourmaline Drugs 0.000 description 1
- 229910052613 tourmaline Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Description
本発明は、ゴム状ラテックス含有発泡スチレン系樹脂成形品及びその製造方法に関する。 The present invention relates to a rubbery latex-containing foamed styrene resin molded article and a method for producing the same.
従来、発泡スチレン系樹脂成形品は優れた断熱性と緩衝特性を有している反面、その特徴である低密度（軽量）のため成形品表面が脆い、機械的強度が低い等の欠点があり、外部からの摩擦や衝撃により容易に擦傷又は破壊される。また、静電気が発生し易く埃が付着しやすい。さらに、油等の汚れや一度使用した後の汚れは発泡体表面に染み込むため水洗浄では除去できない。また、成形品を水中に浸漬すると含水し易い。その結果、発泡倍率が制限されたり、一回使用したら廃棄若しくは限定使用となっている。従ってこれらの欠点を解決してその用途を拡大することが望まれている。 Conventionally, foamed styrenic resin molded products have excellent heat insulation and buffering properties, but have low defects (light weight), which is a characteristic of them, and have disadvantages such as a fragile molded product surface and low mechanical strength. It is easily scratched or destroyed by external friction or impact. In addition, static electricity is easily generated and dust is likely to adhere. In addition, dirt such as oil and dirt once used soaks into the foam surface and cannot be removed by water washing. Moreover, when a molded article is immersed in water, it is easy to contain water. As a result, the expansion ratio is limited, or once used, it is discarded or limited. Therefore, it is desired to solve these drawbacks and expand their applications.
これらの欠点を克服する技術として、発泡性樹脂粒子の分子量、分子量分布、組成、樹脂粒子径等の最適化が図られている。例えば、発泡性スチレン系樹脂を合成する際に、スチレンと共重合可能なモノマー例えばアクリロニトリル、メタクリル酸メチル、ブタジエン、アクリル酸ブチル等を共重合させたり、ポリエチレン又はポリプロピレン等のオレフィン類を共重合させる方法がある。
しかし、共重合化によって、耐熱性、耐溶剤性、成形加工性は改善されても高発泡化、緩衝特性の改良には限界がある。また、コスト高の要因にもなる。
As a technique for overcoming these drawbacks, optimization of the molecular weight, molecular weight distribution, composition, resin particle diameter and the like of the expandable resin particles has been attempted. For example, when synthesizing a foamable styrene resin, a monomer copolymerizable with styrene such as acrylonitrile, methyl methacrylate, butadiene, butyl acrylate, or the like, or an olefin such as polyethylene or polypropylene is copolymerized. There is a way.
However, even if heat resistance, solvent resistance, and molding processability are improved by copolymerization, there is a limit to the improvement of high foaming and buffering characteristics. Moreover, it becomes a factor of high cost.
さらに、押出機にてポリスチレンと相溶性のあるスチレン・ブタジエンゴムを混合・押出してペレット状にし、懸濁重合により発泡性スチレン系樹脂粒子を製造することも実施されているが、前記と同様、高発泡化、緩衝特性の改良には限界がある。 In addition, polystyrene and styrene-butadiene rubber compatible with polystyrene are mixed and extruded into pellets, and foaming styrene resin particles are produced by suspension polymerization. There is a limit to the improvement of foaming and cushioning properties.
また、成形体と樹脂シートの成形品を貼り合わせたり、プラスチックシートと一体成形する技術も提案されている（例えば、特許文献１、特許文献２、特許文献３）。しかし、これらの方法は工数が増えコスト高となる。 Moreover, the technique of bonding a molded object and the molded product of a resin sheet, or integrally forming with a plastic sheet is also proposed (for example, patent document 1, patent document 2, patent document 3). However, these methods increase man-hours and increase costs.
本発明は、機械的強度、耐衝撃性、可とう性、平滑性、耐汚染性、耐吸水性、耐溶剤性等に優れる発泡スチレン系樹脂成形品及びその製造方法を提供することを目的とする。 An object of the present invention is to provide a foamed styrenic resin molded article excellent in mechanical strength, impact resistance, flexibility, smoothness, stain resistance, water absorption resistance, solvent resistance, and the like, and a method for producing the same. To do.
発明者らは、上記問題点を鑑み鋭意研究を行った結果、発泡スチレン系樹脂成形品にゴム状ラテックスを含ませることにより、従来の発泡スチレン系樹脂成形品が有する優れた断熱性と緩衝特性を損なうことなく、高発泡化も可能で機械的強度、耐衝撃性、耐溶剤性、耐熱性等を付与することができることを見出し本発明に至った。 The inventors have conducted extensive research in view of the above problems, and as a result, by including a rubber-like latex in the foamed styrene resin molded product, excellent heat insulating properties and buffering properties of conventional foamed styrene resin molded products. The present invention has been found that high foaming can be achieved without impairing mechanical properties, and mechanical strength, impact resistance, solvent resistance, heat resistance, and the like can be imparted.
本発明によれば、以下の発泡スチレン系樹脂成形品等が提供される。
１．表面にゴム状ラテックスからなるゴム層を有し、前記ゴム状ラテックスは濡れ性向上剤、チキソトロピー性付与剤、染料、顔料、抗菌剤又は鮮度保持剤を含むことができることを特徴とする発泡性スチレン系樹脂粒子。
２．ゴム状ラテックスと発泡性スチレン系樹脂粒子を混合し、前記発泡性スチレン系樹脂粒子の表面をゴム状ラテックスで被覆することを特徴とする１記載の発泡性スチレン系樹脂粒子の製造方法。
３．表面にゴム状ラテックスからなるゴム層を有し、前記ゴム状ラテックスは濡れ性向上剤、チキソトロピー性付与剤、染料、顔料、抗菌剤又は鮮度保持剤を含むことができることを特徴とする予備発泡スチレン系樹脂粒子。
４．発泡性スチレン系樹脂粒子とゴム状ラテックスを混合し、予備発泡することを特徴とする３記載の予備発泡スチレン系樹脂粒子の製造方法。
５．１記載の発泡性スチレン系樹脂粒子を予備発泡することを特徴とする３記載の予備発泡スチレン系樹脂粒子の製造方法。
６．ゴム状ラテックスからなるゴム層を表面に有し、前記ゴム状ラテックスは濡れ性向上剤、チキソトロピー性付与剤、染料、顔料、抗菌剤又は鮮度保持剤を含むことができることを特徴とする発泡スチレン系樹脂成形品。
７．１記載の発泡性スチレン系樹脂粒子を予備発泡、成形又は３記載の予備発泡スチレン系樹脂粒子を成形させて得られることを特徴とする６記載の発泡スチレン系樹脂成形品。
８．表面にゴム状ラテックスを塗布して得られることを特徴とする６記載の発泡スチレン系樹脂成形品。
９．前記ゴム状ラテックスが、合成ゴムラテックス及び／又はアクリル酸エステル共重合体エマルジョンであることを特徴とする６〜８のいずれか一に記載の発泡スチレン系樹脂成形品。
尚、上記１，３，６において、ゴム状ラテックスは乾燥されたものも含む。通常、発泡性樹脂粒子の場合は、ゴム状ラテックスは液状又は乳化状であり、予備発泡粒子の場合は、発泡直後はゴム状ラテックスは液状又はやや乾燥した状態であるが乾燥工程を経て固化され、成形品の場合は、乾燥により固化した状態である。本明細書においてゴム状ラテックスを同様の意味で使用する場合がある。
According to the present invention, the following foamed styrenic resin molded articles and the like are provided.
1. A foam layer characterized in that it has a rubber layer made of rubber latex on the surface, and the rubber latex can contain a wettability improver, a thixotropic agent, a dye, a pigment, an antibacterial agent or a freshness keeping agent . Styrenic resin particles.
2. 2. The method for producing expandable styrene resin particles according to 1, wherein rubber latex and expandable styrene resin particles are mixed and the surface of the expandable styrene resin particles is coated with rubber latex.
3. A pre-foam characterized by having a rubber layer made of a rubber-like latex on the surface, and the rubber-like latex can contain a wettability improver, a thixotropic agent, a dye, a pigment, an antibacterial agent, or a freshness-keeping agent. Styrenic resin particles.
4). 4. The method for producing pre-expanded styrene resin particles according to 3, wherein the expandable styrene resin particles and rubber-like latex are mixed and pre-expanded.
5. The method for producing pre-expanded styrene resin particles according to 3, wherein the expandable styrene resin particles according to 5.1 are pre-expanded.
6 . Has a rubber layer made of a rubber-like latex surface, the rubber-like latex wettability improvers, thixotropic agents, characterized in that it can include dyes, pigments, antimicrobial agents, or freshness-retaining agent originating Foam styrene resin molded product.
7 . 6. A foamed styrene resin molded article according to 6, obtained by pre-expanding or molding the expandable styrene resin particles according to 1, or molding the pre-expanded styrene resin particles according to 3.
8 . 6. The foamed styrene resin molded article according to 6, which is obtained by applying a rubbery latex to the surface.
9 . The rubber-like latex, synthetic rubber latex and / or foam styrene resin molded article according to any one of 6-8, wherein the acrylic acid ester copolymer Emarujo down.
Also it includes the 1,3, Oite to 6, those rubber latex which has been dried. Usually, in the case of expandable resin particles, the rubbery latex is liquid or emulsified. In the case of pre-expanded particles, the rubbery latex is liquid or slightly dried immediately after foaming but is solidified through a drying process. In the case of a molded product, it is in a state solidified by drying. In the present specification, rubbery latex may be used in the same meaning.
本発明によれば、機械的強度、耐衝撃性、可とう性、平滑性、耐汚染性、耐吸水性等に優れる発泡スチレン系樹脂成形品及びその製造方法を提供できる。 According to the present invention, it is possible to provide a foamed styrene resin molded article excellent in mechanical strength, impact resistance, flexibility, smoothness, stain resistance, water absorption resistance, and the like, and a method for producing the same.
以下、本発明の発泡スチレン系樹脂成形品及びその製造方法について詳細に説明する。 Hereinafter, the foamed styrene resin molded article and the method for producing the same of the present invention will be described in detail.
本発明の発泡スチレン系樹脂成形品は、ゴム状ラテックスを内部及び／又は表面に有する。ゴム状ラテックスはゴム層を形成していてもよく、ゴム層は連続層とすることができる。 The foamed styrenic resin molded article of the present invention has rubbery latex inside and / or on the surface. The rubber-like latex may form a rubber layer, and the rubber layer can be a continuous layer.
本発明の発泡スチレン系樹脂成形品自体は特に限定されず、発泡性スチレン系樹脂粒子を所望の倍数に予備発泡した後、加熱発泡成形して得られる成形品、又はスチレン系樹脂を押出発泡により成形したものであってよい。 The foamed styrenic resin molded product itself of the present invention is not particularly limited, and a foamed styrenic resin particle is pre-foamed to a desired multiple and then molded by heating and foaming, or a styrene resin is obtained by extrusion foaming. It may be molded.
本発明で使用する発泡性スチレン系樹脂粒子は、ポリスチレン又はスチレンとこれと共重合可能なモノマーとの共重合体である。スチレンと共重合可能なモノマーとしては、α−メチルスチレン、ビニルトルエン等のスチレン誘導体又はその置換体、メタクリル酸メチル等のメタクリル酸アルキルエステル、アクリロニトリル、ブタジエン、アクリル酸ブチル及びエチレン、プロピレン等のオレフィンがあり、その使用量はモノマーの総量に対し５０質量％未満が好ましいが目的によってはこの限りではない。また、これらの混合物も含まれる。 The expandable styrenic resin particles used in the present invention are polystyrene or a copolymer of styrene and a monomer copolymerizable therewith. As monomers that can be copolymerized with styrene, styrene derivatives such as α-methylstyrene and vinyltoluene or substituted products thereof, alkyl methacrylates such as methyl methacrylate, acrylonitrile, butadiene, butyl acrylate, and olefins such as ethylene and propylene The amount used is preferably less than 50% by weight based on the total amount of monomers, but is not limited to this depending on the purpose. Mixtures of these are also included.
発泡剤としては、プロパン、ブタン、ペンタン、ヘキサン等の脂肪族炭化水素がある。発泡剤をスチレン系樹脂に含浸させる方法としては、懸濁重合法又は押出発泡法があり既に公知の技術である。 Examples of the blowing agent include aliphatic hydrocarbons such as propane, butane, pentane, and hexane. As a method of impregnating a styrene resin with a foaming agent, there are a suspension polymerization method and an extrusion foaming method, which are already known techniques.
本発明で使用するゴム状ラテックスには、合成ゴムラテックス及びアクリル酸エステル共重合体エマルジョンが含まれる。合成ゴムラテックスには、変性アクリロニトリル・ブタジエン共重合体、変性アクリル酸エステル・ブタジエン共重合体、変性スチレン・ブタジエン共重合体、変性メタクリル酸エステル・ブタジエン共重合体等が含まれる。これらのゴム状ラテックスは単独で使用してもよいが目的に応じて混合して使用しても差し支えない。上記のゴム状ラテックスは変性されていてもよく、例えば、接着性や耐熱性向上を目的にカルボキシル基変性やアルコキシシリル基変性等が挙げられる。また、エマルジョンに使用される乳化剤はアニオン、ノニオン、又はソープフリータイプいずれでも構わない。
Rubbery latex used in the present invention include synthetic rubber latex and an acrylic acid ester copolymer Emarujo down. Synthetic rubber latex includes modified acrylonitrile / butadiene copolymer, modified acrylic ester / butadiene copolymer, modified styrene / butadiene copolymer, modified methacrylate ester / butadiene copolymer, and the like. These rubber-like latexes may be used alone, or may be mixed and used according to the purpose. The rubbery latex may be modified, and examples thereof include carboxyl group modification and alkoxysilyl group modification for the purpose of improving adhesiveness and heat resistance. The emulsifier used in the emulsion may be an anion, nonion, or soap-free type.
本発明における発泡性スチレン系樹脂粒子へのゴム状ラテックスの被覆方法として、ゴム状ラテックスをリボンブレンダー、Ｖブレンダー等のブレンダーやヘンシェルミキサー、レディゲミキサー等のミキサーにて混合する方法等が採用できる。ゴム状ラテックスは前記混合方法により各粒子表面に均一に被覆することが好ましい。また、その混合比率は、発泡性スチレン系樹脂粒子１００質量部に対し、好ましくは０．１〜１５質量部であり、特性及び生産性の面から最適な配合は、０．５〜５質量部である。上記方法でゴム状ラテックスを被覆した樹脂粒子は発泡剤が逸散しない範囲内でゴム状ラテックス中の水分を除去させることが望ましい。 As the method of coating the rubbery latex on the expandable styrene resin particles in the present invention, a method of mixing the rubbery latex with a blender such as a ribbon blender or a V blender, a mixer such as a Henschel mixer or a Redige mixer can be adopted. . The rubbery latex is preferably uniformly coated on the surface of each particle by the mixing method. Further, the mixing ratio is preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the expandable styrene resin particles, and the optimum blending from the viewpoint of characteristics and productivity is 0.5 to 5 parts by mass. It is. It is desirable that the resin particles coated with the rubber-like latex by the above-mentioned method remove water in the rubber-like latex within a range where the foaming agent does not escape.
さらに、発泡性スチレン系樹脂粒子にゴム状ラテックスを被覆させる方法として、予備発泡機を使用できる。この方法では、発泡性スチレン系樹脂粒子を、上記混合比率でゴム状ラテックスと共に撹拌装置が備わっている予備発泡機に投入する。予備発泡と同時に効果的に被覆することができる。この場合、ゴム状ラテックスがスチームにより加熱されることにより、乳化破壊を引き起こし水分が除去されて、ラテックス中のゴム成分のみが発泡性スチレン系樹脂粒子に効果的に被覆し、ゴム状ラテックスで被覆された予備発泡スチレン系樹脂粒子が得られる。 Furthermore, a pre-foaming machine can be used as a method of coating expandable styrene resin particles with a rubbery latex. In this method, expandable styrenic resin particles are introduced into a pre-foaming machine equipped with a stirring device together with a rubbery latex at the above mixing ratio. It can be effectively coated simultaneously with the pre-foaming. In this case, when the rubbery latex is heated by steam, the emulsion breaks and moisture is removed, and only the rubber component in the latex effectively coats the expandable styrenic resin particles, and the rubbery latex is coated. Thus obtained pre-expanded styrene resin particles are obtained.
上記のゴム状ラテックスで被覆された発泡性スチレン系樹脂粒子を予備発泡、成形して、又は予備発泡スチレン系樹脂粒子を成形して、ゴム状ラテックスを含む発泡スチレン系樹脂成形品を得ることができる。また、発泡スチレン系樹脂成形品は、成形品を形成した後に、表面をゴム状ラテックスで被覆してもよい。 It is possible to obtain a foamed styrene resin molded product containing a rubbery latex by prefoaming and molding the foamable styrene resin particles coated with the rubbery latex, or by molding the prefoamed styrene resin particles. it can. The foamed styrene resin molded product may be coated with a rubbery latex after the molded product is formed.
発泡スチレン系樹脂成形品にゴム状ラテックスを塗布しゴム層を成形品表面に形成する方法として、刷毛での塗布、スプレーガンによる吹き付け、又はゴム状ラテックスへの成形品の浸漬等何れの方法でも可能である。塗布後、室温〜８０℃で乾燥することでラテックス中の水分を放出できる。成形品とゴム層の密着性を確保するためには成形品の材質に応じたラテックスの選択が重要である。
このときの膜厚は、乾燥前で通常０．１〜１００μｍ、好ましくは５〜７０μｍである。
As a method of applying a rubber latex to a foamed styrene-based resin molded product and forming a rubber layer on the surface of the molded product, any method such as application with a brush, spraying with a spray gun, or immersion of the molded product in a rubbery latex can be used. Is possible. After application, moisture in the latex can be released by drying at room temperature to 80 ° C. In order to ensure the adhesion between the molded product and the rubber layer, it is important to select a latex according to the material of the molded product.
The film thickness at this time is usually 0.1 to 100 μm, preferably 5 to 70 μm before drying.
このように、本発明の成形品は、ゴム状ラテックスを被覆した発泡性スチレン系樹脂粒子を予備発泡、成形して得られる成形品、予備発泡中にゴム状ラテックスを混合被覆した予備発泡粒子を成形して得られる成形品、又は何も混合被覆しない通常のスチレン系樹脂の成形品又は上記の製造過程においてゴム状ラテックスを混合した成形品にゴム状ラテックスを塗布して得られる成形品であり、いずれにおいてもゴムの特徴が発現できる。使用するゴム状ラテックスは目的に応じて選択をすれば良い。特性の異なるゴム状ラテックスの組み合わせが効果的な場合も多い。例えば、スチレン・ブタジエン共重合体で成形品に曲げ強度を付与し、さらにアクリロニトリル・ブタジエン共重合体ラテックスで耐熱性又は耐溶剤性を付与する。これにより用途拡大が図れる。 As described above, the molded product of the present invention is obtained by pre-foaming and molding foamable styrene resin particles coated with rubber-like latex, and pre-foamed particles obtained by mixing and coating rubber-like latex during pre-foaming. A molded product obtained by molding, or a molded product obtained by applying a rubbery latex to an ordinary styrene resin molded product that is not mixed and coated, or a molded product that is mixed with a rubbery latex in the above production process. In any case, the characteristics of rubber can be expressed. What is necessary is just to select the rubber-like latex to be used according to the objective. Often, a combination of rubbery latexes with different properties is effective. For example, a styrene / butadiene copolymer imparts bending strength to the molded article, and acrylonitrile / butadiene copolymer latex imparts heat resistance or solvent resistance. As a result, applications can be expanded.
また、使用するゴム状ラテックスには目的に応じて以下の改質剤を添加することができる。改質剤はゴム状ラテックスとスチレン系樹脂粒子又は発泡樹脂成形品との密着性を改良するための濡れ性向上剤、均一な塗布面を得るためのチキソトロピー性付与剤、ゴム状ラテックスのバインダー機能を生かしての成形品の着色のための染料又は顔料、抗菌性付与のための抗菌剤、鮮度保持のための鮮度保持剤である。改質剤含有ラテックスは、改質目的に応じて、発泡性樹脂粒子又は予備発泡粒子に被覆するか、成形品表面に被覆するか等を選択することができる。
Moreover, the following modifiers can be added to the rubbery latex used depending on the purpose. Modifier thixotropic agent to obtain wettability improver for improving the adhesion between the rubber-like latex and styrene resin particles or the resin foam product, a uniform coated surface of the rubber-like latex binder It is a dye or pigment for coloring a molded product by making use of its function, an antibacterial agent for imparting antibacterial properties, and a freshness retaining agent for maintaining freshness. The modifying agent-containing latex can be selected depending on the purpose of modification, such as whether to coat the expandable resin particles or pre-expanded particles or the surface of the molded product.
以下、実施例により本発明をさらに詳細に説明する。
尚、実施例で使用した発泡性スチレン系樹脂粒子等は以下の通りである。
（１）発泡性スチレン系樹脂粒子
発泡性ポリスチレン樹脂粒子（日立化成工業製 商品名：ハイビーズ ＳＳＢ−ＴＸ−７）（ＥＰＳ）
アクリロニトリル変性発泡性スチレン系樹脂粒子（日立化成工業製 商品名：ハイビーズＧＲ）（ＧＲ）
メタクリル酸メチル変性発泡性スチレン系樹脂粒子（日立化成工業製 商品名：ハイビーズＡＦ）（ＡＦ）
Hereinafter, the present invention will be described in more detail with reference to examples.
The expandable styrene resin particles used in the examples are as follows.
(1) Expandable styrene resin particles Expandable polystyrene resin particles (trade name: High Beads SSB-TX-7, manufactured by Hitachi Chemical Co., Ltd.) (EPS)
Acrylonitrile-modified expandable styrene resin particles (trade name: High Beads GR, manufactured by Hitachi Chemical) (GR)
Methyl methacrylate modified expandable styrene resin particles (trade name: High Beads AF, manufactured by Hitachi Chemical Co., Ltd.) (AF)
（２）ゴム状ラテックス
変性アクリロニトリル・ブタジエン共重合体ラテックス（日本ゼオン製 商品名：Ｎｉｐｏｌ ＳＸ１５０３ ４２％濃度）（ＡＮ・Ｂ）
変性アクリル酸エステル・ブタジエン共重合体ラテックス（日立化成工業製 商品名：ＢＥラテックス ４５％濃度）（ＡＲ・Ｂ）
変性スチレン・ブタジエン共重合体ラテックス（日本ゼオン製 商品名：Ｎｉｐｏｌ ＳＸ１１０５ ４５％濃度）（ＳＴ・Ｂ）
アクリル酸エステル共重合体エマルジョン（日本ゼオン製 商品名：Ｎｉｐｏｌ ＳＸ１７０６ ４８％濃度）（ＡＥ）
カルボキシ変性スチレン・ブタジエン共重合体ラテックス（日本エイアンドエル社製 商品名：ナルスターＳＲ−１０７ ５１％濃度）（ＣＳＴ・Ｂ）
(2) Rubber-like latex Modified acrylonitrile-butadiene copolymer latex (trade name: Nipol SX1503 42% concentration, manufactured by Nippon Zeon) (AN · B)
Modified acrylic ester / butadiene copolymer latex (trade name: BE latex 45% concentration, manufactured by Hitachi Chemical) (AR / B)
Modified Styrene-Butadiene Copolymer Latex (trade name: Nipol SX1105 45% concentration, manufactured by Nippon Zeon) (ST · B)
Acrylic ester copolymer emulsion (product name: Nipol SX1706 48% concentration, manufactured by Nippon Zeon) (AE)
Carboxy-modified styrene / butadiene copolymer latex (product name: Nalstar SR-107 51% concentration, manufactured by Nippon A & L Co.) (CST · B )
（３）改質剤
青色染料（マジックインキ本舗製 商品名：補充用インキ）
赤色染料（マジックインキ本舗製 商品名：補充用インキ）
石英へんがん（会田工業所製 商品名：電気石（２００メッシュスルー））
ジイソオクチルスルホコハク酸ナトリウム（和光純薬工業社製 商品名：エーロゾル０Ｔ）
(3) Modifier Blue dye (Magic Ink Honpo, trade name: supplementary ink)
Red dye (made by Magic Ink Honpo, trade name: supplementary ink)
Quartz cancer (trade name: tourmaline (200 mesh through) manufactured by Aida Kogyo)
Sodium diisooctylsulfosuccinate (trade name: Aerosol 0T, manufactured by Wako Pure Chemical Industries, Ltd.)
実施例１
発泡性ポリスチレン樹脂粒子１０ｋｇに対し変性アクリロニトリル・ブタジエン共重合体ラテックス２００ｇ（２質量部）をＶブレンダーで１０分間混合した。このラテックスを被覆した発泡性ポリスチレン樹脂粒子を予備発泡機（日立化成テクノプラント製 ＨＢＰ−５００）にて嵩発泡倍数がそれぞれ５１、６１、７１倍（密度１９．６、１６．４、１４．１ｋｇ／ｍ３）に予備発泡し、この発泡粒子を１６時間室温にて熟成した。次いで予備発泡粒子を寸法３００ｍｍ（長）×５０ｍｍ（幅）×２０ｍｍ（厚み）の平板状の成形品６個取りの金型を取り付けた成形機（ダイセン工業製 ＶＳ―３００）にてスチーム圧０．０８Ｍｐａで成形を行い、それぞれ５０、６０、７０倍（密度２０．０、１６．７、１４．３ｋｇ／ｍ３）の成形品を各６枚得た。サンプル名をそれぞれＡ、Ｂ、Ｃとした。
Example 1
200 g (2 parts by mass) of modified acrylonitrile-butadiene copolymer latex was mixed with 10 kg of expandable polystyrene resin particles in a V blender for 10 minutes. The foamed polystyrene resin particles coated with this latex were subjected to a bulk foaming factor of 51, 61, 71 times (density 19.6, 16.4, 14.1 kg) by a pre-foaming machine (HBP-500, manufactured by Hitachi Chemical Technoplant), respectively. / M 3 ) and the foamed particles were aged at room temperature for 16 hours. Next, the steam pressure was reduced to 0 with a molding machine (VS-300, manufactured by Daisen Industries Co., Ltd.) on which the pre-expanded particles were fitted with a mold for obtaining 6 flat plate shaped products having dimensions of 300 mm (length) × 50 mm (width) × 20 mm (thickness). Molding was performed at 0.08 Mpa, and six molded products of 50, 60, and 70 times (density 20.0, 16.7, 14.3 kg / m 3 ) were obtained. The sample names were A, B, and C, respectively.
実施例２
発泡性ポリスチレン樹脂粒子５ｋｇを予備発泡機に投入する際に、変性アクリル酸エステル・ブタジエン共重合体ラテックス１５０ｇ（３質量部）を同時に投入し予備発泡中に混合し、６１倍（密度１６．４ｋｇ／ｍ３）に発泡した。実施例１と同様にして１６時間の熟成後、同一成形機にて６０倍（密度１６．７ｋｇ／ｍ３）の成形品６枚を得た。この試験体をＤとした。
Example 2
When 5 kg of expandable polystyrene resin particles are put into a pre-foaming machine, 150 g (3 parts by mass) of a modified acrylic ester / butadiene copolymer latex is simultaneously added and mixed during pre-foaming, 61 times (density 16.4 kg) / M 3 ). After aging for 16 hours in the same manner as in Example 1, six molded articles of 60 times (density 16.7 kg / m 3 ) were obtained using the same molding machine. This specimen was designated as D.
実施例３
発泡性ポリスチレン樹脂粒子を嵩倍数６１倍に予備発泡し、１６時間熟成した後、同一成形機で６０倍（密度１６．７ｋｇ／ｍ３）の成形品を作製した。この成形板の３００ｍｍ×５０ｍｍの両面に、刷毛とベーカーアプリケーター（井元製作所製 商品名：ＢＡＰ−０４）を用いて、変性スチレン・ブタジエン共重合体ラテックスの層厚がそれぞれ２５、５０ミクロンになるように塗布した。次いでこの試験体を６０℃の乾燥室で２時間放置し乾燥した。２５ミクロンの厚みの試験体をＥ（密度１７．８ｋｇ／ｍ３）、５０ミクロンの厚みの試験体をＦ（密度１９．０ｋｇ／ｍ３）とした。Ｅの塗布前と乾燥後の質量差は０．３５ｇ、Ｆの質量差は０．７１ｇであった。
Example 3
The expandable polystyrene resin particles were pre-expanded to a bulk ratio of 61 times and aged for 16 hours, and then a molded product of 60 times (density 16.7 kg / m 3 ) was produced with the same molding machine. Using a brush and a baker applicator (trade name: BAP-04, manufactured by Imoto Seisakusho) on both sides of 300 mm x 50 mm of the molded plate, the layer thickness of the modified styrene / butadiene copolymer latex is 25 and 50 microns, respectively. It was applied to. Subsequently, this test body was left to dry in a 60 degreeC drying chamber for 2 hours. The specimen having a thickness of 25 microns was designated as E (density 17.8 kg / m 3 ), and the specimen having a thickness of 50 microns was designated F (density 19.0 kg / m 3 ). The mass difference before coating E and after drying was 0.35 g, and the mass difference of F was 0.71 g.
実施例４
アクリロニトリル変性発泡性スチレン系樹脂粒子６ｋｇと変性アクリル酸エステル・ブタジエン共重合体ラテックス１８０ｇ（３質量部）を予備発泡機内で混合し、５１倍（密度１９．６ｋｇ／ｍ３）に発泡、１６時間熟成した。実施例１と同一成形機で５０倍（密度２０．０ｋｇ／ｍ３）の成形板６枚を得た。この試験体をＧとした。
Example 4
6 kg of acrylonitrile-modified foamable styrene resin particles and 180 g (3 parts by mass) of a modified acrylate / butadiene copolymer latex are mixed in a pre-foaming machine and foamed 51 times (density 19.6 kg / m 3 ) for 16 hours. Aged. Six molded plates of 50 times (density 20.0 kg / m 3 ) were obtained using the same molding machine as in Example 1. This specimen was designated as G.
実施例５
実施例４において、アクリロニトリル変性発泡性スチレン系樹脂粒子の代わりにメタクリル酸メチル変性発泡性スチレン系樹脂粒子を使用した以外は実施例４と同様にして５０倍（密度２０．０ｋｇ／ｍ３）の成形板６枚を得た。この試験体をＨとした。
Example 5
In Example 4, 50 times (density 20.0 kg / m 3 ) in the same manner as in Example 4 except that methyl methacrylate-modified expandable styrene resin particles were used instead of acrylonitrile-modified expandable styrene resin particles. Six molded plates were obtained. This specimen was designated as H.
実施例６
実施例３で作製した６１倍の予備発泡粒子を用いて、寸法４００ｍｍ（縦）×３３０ｍｍ（横）×１８０ｍｍ（深さ）、肉厚２５ｍｍの容器６個取りの金型を取り付けた成形機（ダイセン工業製 ＤＡＩＹＡ−ＣＶＳ１３００Ｌ２）にてスチーム圧０．０６５ｍＰａで成形し成形品６個を得た（倍数６０倍）（密度１６．７ｋｇ／ｍ３）。質量は１個あたり１４５ｇであった。６個の各成形品の底部に直径０．５ｍｍの針金で３カ所穴を開け貫通させ、それぞれの容器に水を２Ｌ入れ全ての穴から水が滲み出ることを確認した。この６個の成形品から水を除き乾燥させた後、成形品内側の底部に変性アクリロニトリル・ブタジエン共重合体ラテックスを刷毛とベーカーアプリケーターを用いて２５ミクロンの厚みになるように塗布し、６０℃の乾燥室で２時間乾燥した。塗布前と乾燥後の６個の質量差の平均値は１．６ｇであった。この６個の試験体をＩとした。
Example 6
Using the 61 times pre-expanded particles produced in Example 3, a molding machine equipped with a 6-piece container mold having dimensions of 400 mm (length) x 330 mm (width) x 180 mm (depth) and a thickness of 25 mm ( Daisen Kogyo DAIYA-CVS1300L2) was molded at a steam pressure of 0.065 mPa to obtain 6 molded articles (multiple 60 times) (density 16.7 kg / m 3 ). The mass was 145 g per piece. Three holes were drilled through the bottom of each of the six molded products with a wire having a diameter of 0.5 mm, and 2 L of water was put into each container, and it was confirmed that water exuded from all the holes. After removing water from these six molded products and drying them, a modified acrylonitrile-butadiene copolymer latex was applied to the bottom of the molded product inside using a brush and a baker applicator to a thickness of 25 microns, and 60 ° C. For 2 hours. The average value of the six mass differences before coating and after drying was 1.6 g. These six specimens were designated I.
実施例７
実施例１において、変性アクリロニトリル・ブタジエン共重合体ラテックスの代わりに、変性スチレン・ブタジエン共重合体ラテックス２００ｇ（２質量部）に青色染料５ｇを加え、よく混合したものを使用する以外は、実施例１と同様にして６１倍（密度１６．４ｋｇ／ｍ３）に予備発泡し、次いで１６時間熟成し６０倍（密度１６．７ｋｇ／ｍ３）の青色の美粧な成形品を得た。この試験体をＪとした。
Example 7
In Example 1, instead of the modified acrylonitrile-butadiene copolymer latex, Example 5 was used except that 5 g of the blue dye was added to 200 g (2 parts by mass) of the modified styrene-butadiene copolymer latex and mixed well. In the same manner as in No. 1, it was prefoamed 61 times (density 16.4 kg / m 3 ) and then aged for 16 hours to obtain a 60 times (density 16.7 kg / m 3 ) blue cosmetic molded product. This specimen was designated J.
実施例８
実施例３において、変性スチレン・ブタジエン共重合体ラテックス１００ｇに赤色染料２ｇを加えてよく混合したものを、成形板の３００ｍｍ×５０ｍｍの両面に、刷毛とベーカーアプリケーターを用いて５０ミクロンに塗布した以外は、実施例３と同様にして成形品を作製した。この赤色の試験体をＫ（密度１９．０ｋｇ／ｍ３）とした。Ｋの塗布前と乾燥後の質量差は０．７２ｇであった。
Example 8
In Example 3, a mixture of 100 g of modified styrene / butadiene copolymer latex and 2 g of red dye and mixed well was applied to both sides of 300 mm × 50 mm of the molded plate to 50 microns using a brush and a baker applicator. Produced a molded product in the same manner as in Example 3. This red test specimen was designated as K (density 19.0 kg / m 3 ). The mass difference before coating K and after drying was 0.72 g.
実施例９
実施例２において作製した変性アクリル酸エステル・ブタジエン共重合体を含む成形品の３００ｍｍ×５０ｍｍの片面に、刷毛とベーカーアプリケーターを用いて、変性アクリロニトリル・ブタジエン共重合体ラテックスを、層厚が２５ミクロンになるように塗布し、この試験体をＬとした。次いでこの試験体を６０℃の乾燥室で２時間放置し乾燥した。この成形品の塗布前と乾燥後の質量差は０．１８ｇであった。
Example 9
Using a brush and a baker applicator, a modified acrylonitrile / butadiene copolymer latex was coated on one side of 300 mm × 50 mm of the molded article containing the modified acrylic ester / butadiene copolymer prepared in Example 2 with a layer thickness of 25 microns. The test specimen was designated L. Subsequently, this test body was left to dry in a 60 degreeC drying chamber for 2 hours. The difference in mass between the application of the molded product and the dried product was 0.18 g.
実施例１０
実施例１と同じ発泡性スチレン系樹脂粒子４ｋｇとアクリル酸エステル共重合体エマルジョン２００ｇ（５質量部）を、予備発泡機に投入し、７６倍（密度１３．２ｋｇ／ｍ３）に発泡させた。この発泡粒子を１６時間熟成させ実施例１と同一成形機、金型で成形した６個の試験体をＭとした。この成形品は７５倍（密度１３．３ｋｇ／ｍ３）であった。
また、実施例６と同一成形機、金型、成形条件で容器６個（密度１３．３ｋｇ／ｍ３）を得た。この容器の質量は１個当たり１１５ｇであった。この試験体をＮとした。これらの容器には収縮、変形は無かった。
Example 10
4 kg of the same expandable styrene resin particles as in Example 1 and 200 g (5 parts by mass) of an acrylate copolymer emulsion were put into a pre-foaming machine and foamed 76 times (density 13.2 kg / m 3 ). . M was defined as 6 specimens which were aged for 16 hours and molded with the same molding machine and mold as in Example 1. This molded product was 75 times (density 13.3 kg / m 3 ).
In addition, 6 containers (density 13.3 kg / m 3 ) were obtained using the same molding machine, mold, and molding conditions as in Example 6. The mass of this container was 115 g per piece. This specimen was designated N. These containers did not shrink or deform.
実施例１１
実施例３で作製した６１倍の予備発泡粒子を用いて、実施例６と同一条件で成形し６個の成形品（密度１６．７ｋｇ／ｍ３）を得た。質量は１個あたり１４５ｇであった。このうち３個の成形品の底面及び内側の４側面にそれぞれカルボキシ変性スチレン・ブタジエン共重合体ラテックス４０ｇに鮮度保持剤である微粒子の石英へんがん２０ｇを混合したものを刷毛とベーカーアプリケーターを用いて２５ミクロンの厚みになるよう塗布した。これらの成形品を６０℃の乾燥室で２時間乾燥した。塗布前と乾燥後の３個の平均の質量差は、１０．１ｇであった。サンプル名をＯ（密度１７．３ｋｇ／ｍ３）とした。
Example 11
Using the 61 times pre-expanded particles prepared in Example 3, molding was performed under the same conditions as in Example 6 to obtain six molded articles (density 16.7 kg / m 3 ). The mass was 145 g per piece. Of these, a mixture of 40 g of carboxy-modified styrene / butadiene copolymer latex and 20 g of fine-particle quartz carcinoma as a freshness-retaining agent on each of the bottom and four inner sides of three molded articles was used with a brush and a baker applicator. It was applied to a thickness of 25 microns. These molded articles were dried in a 60 ° C. drying room for 2 hours. The average mass difference between the three before coating and after drying was 10.1 g. The sample name was O (density 17.3 kg / m 3 ).
比較例１
実施例１において、変性アクリロニトリル・ブタジエン共重合体ラテックスを混合しない以外は実施例１と同一条件で予備発泡、成形して、それぞれ５０、６０、７０倍の発泡ポリスチレン成形品（密度２０．０、１６．７、１４．３ｋｇ／ｍ３）を各６枚得た。これらをＱ、Ｒ、Ｓとした。
Comparative Example 1
In Example 1, except that the modified acrylonitrile-butadiene copolymer latex is not mixed, pre-foaming and molding are performed under the same conditions as in Example 1, and 50, 60, and 70 times expanded polystyrene molded articles (density 20.0, 16.7 and 14.3 kg / m 3 ) were obtained for each 6 sheets. These were designated as Q, R, and S.
比較例２
実施例４において、変性アクリル酸エステル・ブタジエン共重合体ラテックスを使用しない以外は実施例４と同様にして予備発泡、成形した（密度２０．０ｋｇ／ｍ３）。これをＴとした。
Comparative Example 2
In Example 4, pre-foaming and molding were performed in the same manner as in Example 4 except that the modified acrylic ester / butadiene copolymer latex was not used (density 20.0 kg / m 3 ). This was designated T.
比較例３
実施例５において、変性アクリル酸エステル・ブタジエン共重合体ラテックスを使用しない以外は実施例４と同様にして予備発泡、成形した（密度２０．０ｋｇ／ｍ３）。これをＵとした。
Comparative Example 3
In Example 5, pre-foaming and molding were performed in the same manner as in Example 4 except that the modified acrylic ester / butadiene copolymer latex was not used (density 20.0 kg / m 3 ). This was designated as U.
比較例４
実施例６において用いた予備発泡樹脂粒子を、実施例６と同様にして成形した発泡ポリスチレンの容器６個（密度１６．７ｋｇ／ｍ３）をＶとした。
Comparative Example 4
Six expanded polystyrene containers (density 16.7 kg / m 3 ) obtained by molding the pre-expanded resin particles used in Example 6 in the same manner as in Example 6 were defined as V.
比較例５
実施例１０において、アクリル酸エステル共重合体エマルジョンを使用しない以外は実施例１０と同様にして予備発泡、成形した。平板の６個の試験体をＷ、容器の６個の試験体をＸとした。これら試験体は、７５倍（密度１３．３ｋｇ／ｍ３）であった。またＸの質量の平均は１１６ｇであった。これらの容器には収縮、変形が観察された。
Comparative Example 5
In Example 10, pre-foaming and molding were performed in the same manner as in Example 10 except that the acrylate copolymer emulsion was not used. Six flat specimens were designated as W, and six specimens of the container were designated as X. These specimens were 75 times (density 13.3 kg / m 3 ). The average mass of X was 116 g. Shrinkage and deformation were observed in these containers.
比較例６
実施例１１において、カルボキシ変性スチレン・ブタジエン共重合体ラテックスと石英へんがんを使用しない以外は実施例１１と同様にして作製した３個の容器（密度１６．７ｋｇ／ｍ３）をＹとした。
Comparative Example 6
In Example 11, three containers (density 16.7 kg / m 3 ) prepared in the same manner as in Example 11 except that carboxy-modified styrene / butadiene copolymer latex and quartz carcinoma were not used were defined as Y. .
実施例１〜１２、及び比較例１〜６で得た発泡スチレン系樹脂成形品の評価結果を表１に示す。尚、表１における特性評価の方法は下記のとおりである。 Table 1 shows the evaluation results of the foamed styrene resin molded products obtained in Examples 1 to 12 and Comparative Examples 1 to 6. In addition, the method of characteristic evaluation in Table 1 is as follows.
（１）表面硬度
成形品の表面硬度は、吉田精機製ポリスチレンフォームテスターＰＦＴ−２のセンサを成形品表面に押圧し、その成形品側の指示値で示した。硬度は数値が低いほど硬く、最低値は２０、最大値が８０である。
(1) Surface hardness The surface hardness of the molded product was indicated by an indication value on the molded product side by pressing a sensor of a polystyrene foam tester PFT-2 manufactured by Yoshida Seiki on the surface of the molded product. The lower the numerical value, the harder, the minimum value is 20, and the maximum value is 80.
（２）曲げ強度
ＪＩＳ−Ａ−９５１１に準じて測定した。
(2) Bending strength It measured according to JIS-A-9511.
（３）耐ガソリン、耐トルエン性
ＡＳＴＭ−Ｄ−５４３−５６に準じて測定した。
評価は○：変化無し、△：一部膨潤、×：溶解とした。
(3) Gasoline resistance and toluene resistance Measured according to ASTM-D-543-56.
The evaluation was ○: no change, Δ: partial swelling, x: dissolution.
（４）吸水率
ＪＩＳ−Ａ−９５１１のＡ類に準じて測定した。
(4) Water absorption Measured according to JIS-A-9511 class A.
（５）水漏れ
成形品容器に水２０Ｌ及び赤インク１０ｍＬを入れ２４時間放置した。漏れ、滲みを目視で観察した。結果は、漏れ又は滲みが発生した場合は、その数を分子とし試験した総数を分母とする分数で示した。
(5) Water leakage 20 L of water and 10 mL of red ink were placed in a molded product container and left for 24 hours. Leakage and bleeding were observed visually. The results were expressed as a fraction with the total number tested as the numerator and the denominator as the denominator when leakage or bleeding occurred.
（６）野菜の鮮度試験
実施例１１及び比較例６において作製した容器に、収穫直後のほうれん草２００ｇを入れ発泡スチレン樹脂製の蓋をして、室温で２日間放置し、その鮮度（萎れ状態）を目視で観察した。野菜を冷蔵庫に保管したものを標準とし、冷蔵庫に保管したものと同等のものを○、やや萎びれているものを△、萎びれているものを×とした。
(6) Freshness test of vegetables In the containers prepared in Example 11 and Comparative Example 6, 200 g of spinach immediately after harvesting was put, covered with a foamed styrene resin lid, and allowed to stand at room temperature for 2 days. Was visually observed. The thing which stored the vegetable in the refrigerator was made into the standard, the thing equivalent to what was stored in the refrigerator was set to (circle), the thing slightly deflated was set to (triangle | delta), and the deflated thing was set to x.
本発明の発泡スチレン系樹脂成形品は、機械的強度、耐衝撃性、可とう性、平滑性、耐汚染性、耐吸水性、耐溶剤性等に優れ、様々な用途、例えば、構造部材、断熱材、梱包材、緩衝材、工芸品等、具体的には自動車用フロアスペーサー、ドレンパン、容器、フロート、住宅用建材、浴室部材、棺、車載用デッキボード等に好適に使用できる。 The foamed styrenic resin molded product of the present invention is excellent in mechanical strength, impact resistance, flexibility, smoothness, stain resistance, water absorption resistance, solvent resistance, etc., for various uses such as structural members, It can be suitably used for heat insulating materials, packing materials, cushioning materials, crafts, and the like, specifically, automotive floor spacers, drain pans, containers, floats, residential building materials, bathroom members, firewood, in-vehicle deck boards, and the like.
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